CN113913194A - Fluorine-containing liquid crystal compound and application thereof - Google Patents

Fluorine-containing liquid crystal compound and application thereof Download PDF

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CN113913194A
CN113913194A CN202111234670.6A CN202111234670A CN113913194A CN 113913194 A CN113913194 A CN 113913194A CN 202111234670 A CN202111234670 A CN 202111234670A CN 113913194 A CN113913194 A CN 113913194A
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liquid crystal
fluorine
reaction
crystal compound
containing liquid
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CN113913194B (en
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石志亮
呼建军
张小玲
杭德余
班全志
李小赢
程丹丹
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Anhui Yubei New Material Technology Co ltd
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Beijing Yunji Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • C09K19/3405—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a five-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • C09K19/3405—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a five-membered ring
    • C09K2019/3408—Five-membered ring with oxygen(s) in fused, bridged or spiro ring systems
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Abstract

The invention relates to the technical field of liquid crystal compounds, in particular to a novel fluorine-containing liquid crystal compound and application thereof. The liquid crystal compound provided by the invention has a structure shown in a general formula (I), has high negative dielectric anisotropy, good liquid crystal intersolubility and relatively low rotational viscosity, can improve the performance of a liquid crystal material, and has important application value.

Description

Fluorine-containing liquid crystal compound and application thereof
Technical Field
The invention relates to the technical field of liquid crystal compounds, in particular to a novel fluorine-containing liquid crystal compound and application thereof.
Background
In recent years, liquid crystal display devices have been developed more and more rapidly, and various types of liquid crystal display devices have appeared, such as small-sized liquid crystal display devices for vehicles, portable liquid crystal display devices, ultra-thin liquid crystal display devices, and the like. The development in the art is progressing, taking liquid crystal display as an example, which is characterized by light weight, small occupied space, and convenience in movement, as well as notebook-type personal computers, palm computers, mobile phones, and the like.
The liquid crystal material has great research value and good application prospect in the fields of information display materials, organic optoelectronic materials and the like. At present, the TFT-LCD product technology has matured, and successfully solves the technical problems of viewing angle, resolution, color saturation, brightness, etc., and large-size and medium-and small-size TFT-LCD displays have gradually occupied the mainstream status of flat panel displays in respective fields. Meanwhile, the requirements for display technologies are continuously increasing, for example, a liquid crystal display is required to achieve faster response, and a driving voltage is reduced to reduce power consumption, so that a liquid crystal material is required to have low-voltage driving, fast response, a wide temperature range, good low-temperature stability, and other properties.
The liquid crystal material plays an important role in improving the performance of the liquid crystal display, and particularly, the performance of the liquid crystal display can be obviously improved by reducing the rotational viscosity of the liquid crystal material and improving the dielectric anisotropy delta epsilon of the liquid crystal material. Therefore, in order to improve the properties of liquid crystal materials to meet new requirements, the synthesis of liquid crystal compounds with novel structures and the study of the structure-property relationship have become an important work in the liquid crystal field.
Disclosure of Invention
The invention aims to develop a novel fluorine-containing liquid crystal compound, in particular to a fluorobenzofuran-containing liquid crystal compound which has higher negative dielectric anisotropy, good liquid crystal intersolubility, relatively low rotational viscosity and the like, can improve the performance of a liquid crystal material, and has important application value.
In a first aspect, the present invention provides a fluorine-containing liquid crystal compound having a structure represented by general formula (I):
Figure BDA0003317079310000021
wherein R is1And R2Independently of one another, an alkyl, alkoxy or alkenyl radical having 1 to 12 carbon atoms;
A1、A2and A3Independently of one another, 1, 4-phenylene, 1, 4-cyclohexylene, 1, 4-cyclohexenylene or fluoro-1, 4-phenylene;
Z1、Z2and Z3Independently of each other, represents a single bond, a double bond, an oxygen atom, -CF2O-、-CH2CH2-、-CH2O-、-OCH2-or-CH ═ CH-;
x represents an oxygen atom, a sulfur atom, -CH2-、-CF2-or-CHF-;
m, n, p independently of one another represent 0, 1 or 2.
Wherein the fluoro 1, 4-phenylene is mono-fluoro 1, 4-phenylene, difluoro 1, 4-phenylene, trifluoro 1, 4-phenylene or tetrafluoro 1, 4-phenylene; preferably, the fluoro 1, 4-phenylene is mono-fluoro 1, 4-phenylene or di-fluoro 1, 4-phenylene.
As a preferred embodiment of the present invention, said X represents an oxygen atom.
As a preferred embodiment of the present invention, said m, n, p represent independently of each other 0 or 1.
As a preferred embodiment of the present invention, said R1And R2Independently of one another, an alkyl, alkoxy or alkenyl radical having 1 to 5 carbon atoms.
Further preferably, said R1And R2Independently of one another, represents an alkyl, alkoxy or alkenyl group having 2 to 5 carbon atoms.
More preferably, said R1And R2Independently of one another, from the group consisting of ethyl, n-propyl, n-butyl, n-pentyl, ethoxy.
As a preferred embodiment of the present invention, Z is1、Z2And Z3All represent single bonds.
In a preferred embodiment of the present invention, the fluorine-containing liquid crystal compound is selected from the group consisting of structures represented by any one of the following general formulae I-1 to I-17:
Figure BDA0003317079310000031
Figure BDA0003317079310000041
Figure BDA0003317079310000051
Figure BDA0003317079310000061
wherein, in the general formulas I-1 to I-17, R is1And R2Each independently of the other represents an alkyl, alkoxy or alkenyl group having 1 to 5 carbon atoms.
More preferably, in the above general formulae I-1 to I-17, R is1And R2Each independently of the other represents an alkyl, alkoxy or alkenyl group having 2 to 5 carbon atoms.
More preferably, in the above general formulae I-1 to I-17, R is1And R2Are each independently of the others selected from ethyl, n-propyl, n-butyl, n-pentyl, ethoxy.
As a preferred embodiment of the present invention, the fluorine-containing liquid crystal compound is any compound selected from the group consisting of compounds represented by the following structures:
Figure BDA0003317079310000062
Figure BDA0003317079310000071
Figure BDA0003317079310000081
Figure BDA0003317079310000091
Figure BDA0003317079310000101
Figure BDA0003317079310000111
in a second aspect, the invention provides a preparation method of the fluorine-containing liquid crystal compound, which can be synthesized by the following methods according to different substituents in the general formula.
In the first method, when m, n and p in the formula (I) are all 0, the fluorine-containing liquid crystal compound has the formula:
Figure BDA0003317079310000121
the synthetic route is as follows:
Figure BDA0003317079310000122
the synthesis method comprises the following steps:
(1) to be provided with
Figure BDA0003317079310000123
And
Figure BDA0003317079310000124
prepared by Suzuki reaction as raw material
Figure BDA0003317079310000125
(2) The above-mentioned
Figure BDA0003317079310000126
Under alkaline conditions, a ring closure reaction is carried out to obtain
Figure BDA0003317079310000127
Wherein, the
Figure BDA0003317079310000128
And
Figure BDA0003317079310000129
the reaction molar ratio of (1) to (0.9-1.2) and the reaction temperature of 60-120 ℃.
The above-mentioned
Figure BDA00033170793100001210
The molar ratio of the alkali to the alkali is 1: 1-4, and the reaction temperature is 70-150 ℃; wherein the adopted alkali is any one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and potassium tert-butoxide, and the preferred alkali is potassium tert-butoxide and/or potassium carbonate.
In the second method, when n is 0 and m and p are not both 0 in the general formula (I), the synthetic route is as follows:
Figure BDA0003317079310000131
the synthesis method comprises the following steps:
(1) to be provided with
Figure BDA0003317079310000132
And
Figure BDA0003317079310000133
prepared by Suzuki reaction as raw material
Figure BDA0003317079310000134
(2) The above-mentioned
Figure BDA0003317079310000135
Under alkaline conditions, a ring closure reaction is carried out to obtain
Figure BDA0003317079310000136
Wherein the content of the first and second substances,
Figure BDA0003317079310000137
and
Figure BDA0003317079310000138
the reaction molar ratio of (1) to (0.9-1.2) and the reaction temperature of 60-120 ℃.
Wherein, the
Figure BDA0003317079310000141
The molar ratio of the alkali to the alkali is 1: 1-4, and the reaction temperature is 70-150 ℃; wherein the adopted alkali is any one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and potassium tert-butoxide, and the preferred alkali is potassium tert-butoxide and/or potassium carbonate.
In the third method, when n is 1, m and p are 0 at the same time, and Z is2Represents a single bond, A2When represents 1, 4-cyclohexylene, the structural formula is:
Figure BDA0003317079310000142
the synthetic route is as follows:
Figure BDA0003317079310000143
the synthesis method comprises the following steps:
(1) to be provided with
Figure BDA0003317079310000144
With an organolithium reagent and then with
Figure BDA0003317079310000145
Reacting, then dehydrating to obtain
Figure BDA0003317079310000146
(2) The above-mentioned
Figure BDA0003317079310000151
Through hydrogenation reaction, obtain
Figure BDA0003317079310000152
Wherein the content of the first and second substances,
Figure BDA0003317079310000153
an organic lithium reagent,
Figure BDA0003317079310000154
The reaction molar ratio of (1) to (1.0-4.0) to (0.8-1.5), and the reaction temperature of-50 to-100 ℃; the organic lithium reagent is selected from any one or more of sec-butyl lithium, tert-butyl lithium and n-butyl lithium; the dehydrating agent used for dehydration is any one or more of p-toluenesulfonic acid, potassium bisulfate and sodium bisulfate.
The hydrogenation reaction in the second step adopts any one or more of palladium carbon, ruthenium carbon and nickel as catalyst, and the dosage of the catalyst is
Figure BDA0003317079310000155
0.1-10% of mole number.
In the above respective production methods, the R1And R2As defined above.
The liquid crystal compound can be stably and efficiently obtained by the preparation method.
In a third aspect, the invention provides a liquid crystal material composition, which comprises the fluorine-containing liquid crystal compound. The fluorine-containing liquid crystal compound is 0.1-60% by mass, preferably 1-40% by mass, and more preferably 3-25% by mass of the composition.
In a fourth aspect, the invention provides the application of the fluorine-containing liquid crystal compound or the liquid crystal material composition in the liquid phase display field.
As a preferred embodiment, the invention provides the application of the fluorine-containing liquid crystal compound or the liquid crystal material composition in a liquid phase display device.
Preferably, the liquid crystal display device includes, but is not limited to, TN, ADS, VA, PSVA, FFS, IPS, and the like liquid crystal displays.
The invention provides a novel fluorine-containing liquid crystal compound, in particular to a fluorobenzofuran-containing liquid crystal compound which has higher negative dielectric anisotropy, good liquid crystal intersolubility, relatively low rotational viscosity and the like, is required by liquid crystal material improvement and has important application value.
The liquid crystal compound or the composition containing the liquid crystal compound has extremely high negative dielectric anisotropy and low rotational viscosity, so that the driving voltage is effectively reduced, the response speed of a liquid crystal display device is improved, and the liquid crystal compound or the composition containing the liquid crystal compound has the advantages of moderate optical anisotropy value, high charge retention rate and the like, and is a liquid crystal material with excellent performance.
Detailed Description
The technical solution of the present invention will be explained in detail below. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The starting materials are commercially available from the open literature unless otherwise specified.
Example 1
The liquid crystal compound prepared in this example has the structural formula:
Figure BDA0003317079310000161
the synthetic route is as follows:
Figure BDA0003317079310000162
the method comprises the following specific steps:
(1) synthesis of Compound LC-01-1: under the protection of nitrogen, 22g (0.1mol) of 2,3, 4-trifluoro-4-ethoxyphenylboronic acid, 50ml of ethanol, 100ml of toluene, 50ml of water, 13.4g (0.16mol) of sodium bicarbonate and 21.4g (0.1mol) of 2-hydroxy-3-propylbromobenzene are added into a reaction bottle, the temperature is raised to 50 ℃, 0.01g of dichloro-di-tert-butyl- (4-dimethylaminophenyl) phosphine palladium is added, and the temperature is continuously raised to 70 ℃ to 75 ℃ for refluxing for 2 hours. Work-up after the reaction gave 27.9g of a white solid in 90% yield. The white solid obtained, LC-01-1, was analyzed by GC-MS and the product had an M/z of 310 (M)+)。
(2) Synthesis of Compound LC-01: under the protection of nitrogen, 27.9g of compound LC-01-1(0.09mol), 200ml of N-N-dimethylformamide and 20.7g (0.15mol) of potassium carbonate are added into a reaction flask, and the mixture is heated to 110 ℃ to 120 ℃ for reaction for more than 4 hours. Work-up after the reaction gave 24g of a white solid in 92% yield. The white solid obtained, LC-01, was analyzed by GC-MS and the product had an M/z of 290 (M)+)。
Example 2
The liquid crystal compound prepared in this example has the structural formula:
Figure BDA0003317079310000171
the synthetic route is as follows:
Figure BDA0003317079310000172
the method comprises the following specific steps:
(1) compound LC-02-1, synthesis: under the protection of nitrogen, 22g (0.1mol) of 2,3, 4-trifluoro-4-ethoxyphenylboronic acid, 60ml of ethanol, 120ml of toluene, 60ml of water, 22g (0.16mol) of potassium carbonate and 29.6g (0.1mol) of trans-3-propylcyclohexyl-2-hydroxy bromobenzene are added into a reaction bottle, the temperature is raised to 50 ℃, 0.01g of dichloro-di-tert-butyl- (4-dimethylaminophenyl) phosphine palladium is added, and the temperature is continuously raised to 70 ℃ to 75 ℃ for refluxing for 2 hours. Work-up after the reaction gave 35.3g of a white solid in 90% yield. The white solid obtained, LC-02-1, was analyzed by GC-MS and the M/z of the product was 392 (M)+)。
(2) Synthesis of Compound LC-02: under the protection of nitrogen, 35.3g of compound LC-02-1(0.09mol), 260ml of N-N-dimethylformamide and 12.3g (0.11mol) of potassium tert-butoxide are added into a reaction flask, and the temperature is raised to 110 ℃ to 120 ℃ for reaction for more than 4 hours. Work-up after the reaction gave 31.8g of a white solid in 95% yield. The white solid obtained, LC-02, was analyzed by GC-MS and the product had an M/z of 372 (M)+)。
Example 3
The liquid crystal compound prepared in this example has the structural formula:
Figure BDA0003317079310000181
the synthetic route is as follows:
Figure BDA0003317079310000182
the method comprises the following specific steps:
(1) synthesis of Compound LC-03-1: under the protection of nitrogen, 22g (0.1mol) of 2,3, 4-trifluoro-4-ethoxyphenylboronic acid, 60ml of ethanol, 120ml of toluene, 60ml of water, 22g (0.16mol) of potassium carbonate and 29g (0.1mol) of 4-propylphenyl-2-hydroxy bromobenzene are added into a reaction bottle, the temperature is raised to 50 ℃, 0.01g of dichloro-di-tert-butyl- (4-dimethylaminophenyl) phosphine palladium is added, and the temperature is continuously raised to 70 ℃ to 75 ℃ for refluxing for 2 hours. Work-up after the reaction gave 34.7g of a white solid in 90% yield. The white solid LC-03-1 obtained was analyzed by GC-MS and the product had an M/z of 386 (M)+)。
(2) Synthesis of Compound LC-03: under the protection of nitrogen, 34.7g of compound LC-03-1(0.09mol), 260ml of N-N-dimethylformamide and 12.3g (0.11mol) of potassium tert-butoxide are added into a reaction flask, and the temperature is raised to 110 ℃ to 120 ℃ for reaction for more than 4 hours. Work-up after the reaction gave 31.2g of a white solid in 95% yield. The white solid obtained, LC-03, was analyzed by GC-MS and the product had an M/z of 366 (M)+)。
Example 4
The liquid crystal compound prepared in this example has the structural formula:
Figure BDA0003317079310000183
the synthetic route is as follows:
Figure BDA0003317079310000191
the method comprises the following specific steps:
(1) synthesis of Compound LC-04-1: under the protection of nitrogen, adding 23.2(0.10mol) of 2, 3-difluoro-9-ethyl-dibenzofuran and 180ml of tetrahydrofuran into a reaction bottle, controlling the temperature to be-75 to-85 ℃, dropwise adding 0.12mol of n-butyl lithium n-hexane solution, keeping the temperature for 2 hours after dropwise adding, controlling the temperature to be-75 to-85 ℃, dropwise adding 14g of 4-propylcyclohexyl ketone (0.10mol), and naturally returning the temperature to-60 ℃ and keeping the temperature for 2 hours. Adding 200ml of water for quenching reaction, adding 160ml of toluene, washing with water, separating liquid, adding 5g of p-toluenesulfonic acid, refluxing, separating water for 6 hours, and performing conventional aftertreatment to obtain 24.8g of light yellow solid, namely a compound LC-04-1, GC: 99.8% and a yield of 70.0%. The solid LC-04-1 obtained was analyzed by GC-MS and the product had an M/z of 354 (M)+)。
(2) Synthesis of Compound LC-04: under the protection of nitrogen, 24.8g of compound LC-04-1(0.07mol), 160ml of toluene, 40ml of ethanol, 2.5g of 5% palladium carbon and 0.5MPa of hydrogen pressure are added into a hydrogenation kettle, the temperature is raised to 40-60 ℃, and the reaction is carried out for more than 4 hours. Work-up after the reaction gave 15g of a white solid in 60% yield. The white solid obtained LC-04 was subjected to GC-MSAnalysis showed that the M/z of the product was 356 (M)+)。
In the preparation process, the conventional post-treatment is involved if necessary, and the conventional post-treatment specifically comprises the following steps: extracting with dichloromethane, ethyl acetate or toluene, separating, washing with water, drying, evaporating with vacuum rotary evaporator, and purifying the product by vacuum distillation or recrystallization and/or chromatographic separation.
The liquid crystal compounds prepared in examples 1 to 4 of the present invention were subjected to a mixed crystal test as described below. According to the conventional detection method in the field, various performance parameters of the liquid crystal compound are obtained through linear fitting, wherein the specific meanings of the performance parameters are as follows:
n represents the crystalline to nematic melting point (. degree. C.) of the liquid crystal;
CP represents the clearing point of the liquid crystal;
Δ n represents optical anisotropy (25 ℃);
Δ ε represents the dielectric anisotropy (25 ℃, 1000 Hz);
γ 1 represents the rotational viscosity (mPa.s, 25 ℃).
The liquid crystal monomers in the following mixed crystal examples can be synthesized by a known method or commercially available.
Mixed crystal example 1
The liquid crystal compound provided in embodiment 1 of the present invention and other liquid crystal monomers are prepared into a mixed crystal composition, and the mixture ratio and the detection results of the components are shown in table 1 below.
The liquid crystal compound of example 1 in table 1 was replaced with comparative compound 1, of the formula:
Figure BDA0003317079310000201
in comparison with the compound 1, which is a compound,
thus obtaining a comparative example, and the proportion and the detection result of the components of the comparative example are shown in the table 2.
TABLE 1
Figure BDA0003317079310000202
TABLE 2
Figure BDA0003317079310000211
Mixed crystal example 2
The liquid crystal compound provided by embodiment 3 of the present invention and other liquid crystal monomers are prepared into a mixed crystal composition, and the mixture ratio and the detection results of the components are shown in table 3 below.
The liquid crystal compound of example 3 in table 3 was substituted for comparative compound 2, the structural formula is as follows:
Figure BDA0003317079310000212
the compound of reference 2 was used as a reaction medium,
thus, comparative examples were obtained, and the proportions of the components and the test results of the comparative examples are shown in Table 4.
TABLE 3
Figure BDA0003317079310000221
TABLE 4
Figure BDA0003317079310000231
Mixed crystal example 3
The liquid crystal compound provided in embodiment 4 of the present invention and other liquid crystal monomers are prepared into a mixed crystal composition, and the mixture ratio and the detection results of the components are shown in table 5 below.
The liquid crystal compound of example 4 in table 5 was replaced with comparative compound 3, of the following structural formula:
Figure BDA0003317079310000241
in comparison with the compound 3, which was a,
thus, comparative examples were obtained, and the proportions of the components and the test results of the comparative examples are shown in Table 6.
TABLE 5
Figure BDA0003317079310000242
TABLE 6
Figure BDA0003317079310000251
As is apparent from the detection results in tables 1 to 6, when the compound of the present invention is specifically applied to a liquid crystal composition of a conventional system, it is found that the compound can improve the dielectric anisotropy Δ ∈ of the liquid crystal composition, while maintaining a low rotational viscosity γ 1 and a suitable refractive index anisotropy Δ n, and the obtained liquid crystal composition has a significant fast response characteristic and a low voltage driving characteristic.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. A fluorine-containing liquid crystal compound characterized by having a structure represented by the general formula (I):
Figure FDA0003317079300000011
wherein R is1And R2Independently of one another, an alkyl, alkoxy or alkenyl radical having 1 to 12 carbon atoms;
A1、A2and A3Independently of one another, 1, 4-phenylene, 1, 4-cyclohexylene, 1, 4-cyclohexenylene or fluoro-1, 4-phenylene;
Z1、Z2and Z3Independently of one another, represents a single bond, a double bond,Oxygen atom, -CF2O-、-CH2CH2-、-CH2O-、-OCH2-or-CH ═ CH-;
x represents an oxygen atom, a sulfur atom, -CH2-、-CF2-or-CHF-;
m, n, p independently of one another represent 0, 1 or 2.
2. A compound according to claim 1, wherein X represents an oxygen atom.
3. A compound according to claim 1 or 2, characterized in that m, n, p represent independently of each other 0 or 1; and/or the presence of a gas in the gas,
the R is1And R2Independently of one another, an alkyl, alkoxy or alkenyl radical having 1 to 5 carbon atoms.
4. A compound according to any one of claims 1 to 3, wherein Z is1、Z2And Z3Represents a single bond.
5. The compound of claim 1, wherein the fluorine-containing liquid crystal compound is selected from the structures represented by any one of the following general formulae I-1 to I-17:
Figure FDA0003317079300000012
Figure FDA0003317079300000021
Figure FDA0003317079300000031
Figure FDA0003317079300000041
Figure FDA0003317079300000051
wherein, in the above general formula, R is1And R2Each independently of the other represents an alkyl, alkoxy or alkenyl group having 1 to 5 carbon atoms;
preferably, said R is1And R2Each independently of the other represents an alkyl, alkoxy or alkenyl group having 2 to 5 carbon atoms.
6. The compound of claim 1 or 5, wherein the fluorine-containing liquid crystal compound is selected from the compounds represented by the following structural formulas:
Figure FDA0003317079300000052
Figure FDA0003317079300000061
Figure FDA0003317079300000071
Figure FDA0003317079300000081
Figure FDA0003317079300000091
Figure FDA0003317079300000101
7. a method for producing a fluorine-containing liquid crystal compound according to claim 1, characterized by synthesizing by:
when m, n and p in the general formula (I) are all 0, the fluorine-containing liquid crystal compound has the general formula:
Figure FDA0003317079300000111
the synthetic route is as follows:
Figure FDA0003317079300000112
the synthesis method comprises the following steps:
to be provided with
Figure FDA0003317079300000113
And
Figure FDA0003317079300000114
prepared by Suzuki reaction as raw material
Figure FDA0003317079300000115
The above-mentioned
Figure FDA0003317079300000116
Under alkaline conditions, a ring closure reaction is carried out to obtain
Figure FDA0003317079300000117
Wherein, the
Figure FDA0003317079300000118
And
Figure FDA0003317079300000119
the reaction molar ratio of (1) to (0.9-1.2) and the reaction temperature of 60-120 ℃; and/or the presence of a gas in the gas,
the above-mentioned
Figure FDA00033170793000001110
The molar ratio of the alkali to the alkali is 1: 1-4, and the reaction temperature is 70-150 ℃; wherein the adopted alkali is any one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and potassium tert-butoxide, and the preferred alkali is potassium tert-butoxide and/or potassium carbonate;
when n is 0 and m and p are not 0 simultaneously in the general formula (I), the synthetic route is as follows:
Figure FDA0003317079300000121
the synthesis method comprises the following steps:
to be provided with
Figure FDA0003317079300000122
And
Figure FDA0003317079300000123
prepared by Suzuki reaction as raw material
Figure FDA0003317079300000124
The above-mentioned
Figure FDA0003317079300000125
Under alkaline conditions, a ring closure reaction is carried out to obtain
Figure FDA0003317079300000126
Wherein the content of the first and second substances,
Figure FDA0003317079300000127
and
Figure FDA0003317079300000128
the reaction molar ratio of (1) to (0.9-1.2) and the reaction temperature of 60-120 ℃; and/or the presence of a gas in the gas,
the above-mentioned
Figure FDA0003317079300000131
The molar ratio of the alkali to the alkali is 1: 1-4, and the reaction temperature is 70-150 ℃; wherein the adopted alkali is any one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and potassium tert-butoxide, and the preferred alkali is potassium tert-butoxide and/or potassium carbonate;
when n is 1, m and p are simultaneously 0, and Z is2Represents a single bond, A2When represents 1, 4-cyclohexylene, the structural formula is:
Figure FDA0003317079300000132
the synthetic route is as follows:
Figure FDA0003317079300000133
the synthesis method comprises the following steps:
to be provided with
Figure FDA0003317079300000134
With an organolithium reagent and then with
Figure FDA0003317079300000135
Reacting, then dehydrating to obtain
Figure FDA0003317079300000136
The above-mentioned
Figure FDA0003317079300000137
Through hydrogenation reaction, obtain
Figure FDA0003317079300000138
Wherein the content of the first and second substances,
Figure FDA0003317079300000141
an organic lithium reagent,
Figure FDA0003317079300000142
The reaction molar ratio of (1) to (1.0-4.0) to (0.8-1.5), and the reaction temperature of-50 to-100 ℃; the organic lithium reagent is selected from any one or more of sec-butyl lithium, tert-butyl lithium and n-butyl lithium; the dehydrating agent used for dehydration is any one or more of p-toluenesulfonic acid, potassium bisulfate and sodium bisulfate; and/or the catalyst adopted in the hydrogenation reaction is any one or more of palladium carbon, ruthenium carbon and nickel.
8. A liquid crystal material composition, characterized in that the liquid crystal material composition comprises the fluorine-containing liquid crystal compound according to any one of claims 1 to 6; the fluorine-containing liquid crystal compound is 0.1-60% by mass, preferably 1-40% by mass, and more preferably 3-25% by mass of the composition.
9. Use of the fluorine-containing liquid crystal compound according to any one of claims 1 to 6 or the liquid crystal material composition according to claim 8 in the field of liquid phase display.
10. Use of the fluorine-containing liquid crystal compound according to any one of claims 1 to 6 or the liquid crystal material composition according to claim 8 in a liquid crystal display device; preferably, the liquid crystal display device comprises TN, ADS, VA, PSVA, FFS and IPS liquid crystal displays.
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